Benzoylpyrazole derivatives having specific substituents and herbicide

ABSTRACT

The present invention is directed to a compound of formula (1);    &lt;IMAGE&gt;  (1)  wherein R1 and R2 are each independently a halogen atom, a C1-6 alkyl, a C1-6 haloalkyl, a C1-6 alkylsulfonyl or the like, R3 is a di-C1-6 alkoxymethyl, a di-C1-6 alkylthiomethyl, and R4 and R5 are each independently hydrogen, a C1-6 alkyl, a C2-6 alkenyl or the like, and a salt thereof, and a herbicide comprising the said compound and/or the salt.

FIELD OF THE INVENTION

The present invention relates to novel a benzoylpyrazole derivativehaving a specific substituent and a herbicide comprising saidbenzoylpyrazole derivative as its active component.

BACKGROUND ART

As a herbicide comprising a compound having a pyrazole skeleton whereina benzoyl group is substituted to the 4th position of a pyrazole ring,the following compound of formula (I); ##STR2## is disclosed in JapanesePatent Laid-open No. Hei 2-173 Gazette, and another compound of formula(II); ##STR3## is disclosed in Japanese Patent Laid-open No. Hei7-309869 Gazette.

Further, in WO 96/26206 Gazette, a compound of formula III!; ##STR4## isalso disclosed.

It is an object of the present invention to provide a herbicide whichcan be advantageously manufactured in an industrial scale, having firmherbicidal activity at a lower dose thereof and having excellentselectivity in its herbicidal activity that does not give harmful effecton crops.

DISCLOSURE OF THE INVENTION

The present invention is directed to a compound of formula (I); ##STR5##wherein R¹ and R² are each independently hydrogen, a halogen atom,nitro, cyano, a C₁₋₆ alkyl, a C₁₋₆ alkoxy, a C₁₋₆ haloalkyl, a C₁₋₆haloalkoxy, a C₁₋₆ alkylthio, a C₁₋₆ alkylsulfinyl or a C₁₋₆alkylsulfonyl;

R³ is formyl, a di-C₁₋₆ alkoxymethyl or a di-C₁₋₆ alkoxythiomethyl;

R⁴ and R⁵ are each independently hydrogen, a C₁₋₆ alkyl, a C₁₋₆haloalkyl, a C₂₋₆ alkenyl, a C₂₋₆ alkynyl or a C₃₋₈ cycloalkyl, or asalt thereof, and a herbicide comprising said compound(s) or saidsalt(s) thereof.

As an example for the halogen atom represented by R¹ and R², chlorine,bromine, fluorine and the like are given. In addition, as an example forthe C₁₋₆ alkyl represented by the same, methyl, ethyl, propyl,isopropyl, butyl, s-butyl, t-butyl and the like are given; as an examplefor the C₁₋₆ alkoxy, methoxy, ethoxy, propoxy, isopropoxy, butoxy,t-butoxy and the like are given; as an example for the C₁₋₆ haloalkyl,fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl,trifluoromethyl, difluorochloromethyl, fluorochloromethyl,trichloromethyl, tribromomethyl, trifluoroethyl, pentafluoroethyl andthe like are given; and as an example for the C₁₋₆ haloalkoxy,trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, trichloromethoxy,difluoromethoxy and the like are given. Furthermore, as an example forthe C₁₋₆ alkylthio, methylthio, ethylthio, propylthio, isopropylthio andthe like are given; as an example for the C₁₋₆ alkylsulfinyl,methylsulfinyl, ethylsulfinyl and the like are given; and as an examplefor the C₁₋₆ alkylsulfonyl, methylsulfonyl, ethylsulfonyl and the likeare given.

Whereas, as an example for the di-C₁₋₆ alkoxymethyl represented by R³,dimethoxymethyl, diethoxymethyl, dipropoxymethyl, diisopropoxymethy 1,dibutoxymethyl, di-t-butoxymethyl and the like are given; and as anexample for the di-C₁₋₆ alkylthiomethyl, dimethylthiomethyl,diethylthiomethyl, dipropylthiomethyl, diisopropylthiomethyl,dibutylthiomethyl, di-t-butylthiomethyl and the like are given.

Further, as an example for the C₁₋₆ alkyl represented by R⁴ and R⁵,methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl and the likeare given; as an example for the C₁₋₆ haloalkyl, fluoromethyl,1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl,difluorochloromethyl, fluorochloromethyl, trichloromethyl,tribromomethyl, trifluoroethyl, pentafluoroethyl and the like are given;as an example for the C₂₋₆ alkenyl, vinyl, 1-propenyl, allyl, crotyl,butadienyl and the like are given; as an example for the C₂₋₆ alkynyl,ethynyl, 1-propynyl, 2-propynyl, and the like are given; and as anexample for the C₃₋₈ cycloalkyl, cyclopropyl, cyclopentyl, cyclohexyland the like are given.

In the compounds according to the present invention and intermediatecompounds therefor as described hereunder, carbon atom numbers beingcontained in substituents are in a range of either from 1 to 6 (C₁₋₆) or2 to 6 (C₂₋₆), and preferably either from 1 to 4 (C₁₋₄) or 2 to 4(C₂₋₄). The same is applied to the following description.

The compounds according to the present invention can be manufacturedpursuant to the following manufacturing method.

Manufacturing Method (i) ##STR6##

In the manufacturing method described above, R¹, R², R⁴ and R⁵ are asdefined above, Q is a lower alkyl, Z is oxygen or sulphur, and M is alower alkyl.

As indicated in the reaction formula described above, a compound offormula (6a) and/or a compound of formula (6b) are manufactured byfirstly converting 3-formyl benzoate ester of formula (2) to an acetalcompound of formula (4) to obtain a compound of formula (5), thensubjecting the compound of formula (5) to a reaction withhydroxypyrazole of formula (3). Consequently, the objective compound offormula (1--1) can be manufactured from the compound of formula (6a)and/or the compound of formula (6b) via a rearrangement reaction.

The compound of formula (4) can be manufactured by proceeding a reactionof the compound of formula (2) in an amount of 1 mol with any of analcohol, such as methanol and ethanol, an ortho-ester, such as methylorthoformate, and a mercaptan, such as methyl mercaptan and ethylmercaptan, in an amount of 1 mol, or an excessive amount can be used foreither of the compounds to be used for the reaction, according to acustomary method for chemical synthesis, such as a method described inOrg. Synth., III, 644 (1955).

The compound of formula (5) can be manufactured from the compound offormula (4) by using an alkali, such as sodium hydroxide, according to acustomary method for chemical synthesis.

The compounds of formulas (6a) and (6b) can be obtained by subjectingthe compound of formula (5) and the compound of formula (3) to areaction in the presence of a dehydrating and condensing agent, such asdicyclohexylcarbodiimide (DCC). As an example for a solvent to be usedin the reaction with DCC or the like, methylene chloride, chloroform,toluene, ethyl acetate, N,N-dimethylformamide (DMF), tetrahydrofuran(THF), 1,2-dimethoxy ethane, acetonitrile, t-amyl alcohol and the likeare given. The mixture prepared for the reaction is stirred at atemperature range of from -10° C. to a boiling point of a solvent used,and the reacted-product is further treated according to a customarymethod for after-treatment.

The compound of formula (6a) and the compound of formula (6b) are usableas a mixture for the subsequent rearrangement reaction.

The rearrangement reaction is proceeded in the presence of a cyanide anda mild base. More particularly, The compound of formula (1--1) can beobtained by reacting a mixture of the compounds of formula (6a) and (6b)in an amount of 1 mol with a base in an amount of from 1 to 4 mol,preferably from 1 to 2 mol, and a cyanide in an amount of from 0.01 to1.0 mol, preferably from 0.05 to 0.2 mol.

As an example for the base used in the reaction as described above, analkali metal hydroxide, such as KOH and NaOH, an alkali metal carbonate,such as sodium carbonate and potassium carbonate, an alkaline earthmetal hydroxide, such as calcium hydroxide and magnesium hydroxide, analkaline earth metal carbonate, such as calcium carbonate, a tertiaryamine, such as triethylamine and diisopropyl ethylamine, an organicbase, such as pyridine and sodium phosphate, and the like are given.

Also, as an example for the cyanide used as described above, potassiumcyanide, sodium cyanide, acetone cyanohydrin, hydrogen cyanide, apolymer holding potassium cyanide and the like are given. It ispreferable to add a small amount of a phase-transfer catalyst, such ascrown ether, to complete a reaction in a shorter time. It is alsopreferable to proceed the reaction at a temperature lower than 80° C.,and more preferably in a range of from an ambient temperature to 40° C.A solvent usable in the reaction are toluene, acetonitrile, 1,2-dichloroethane, methylene chloride, chloroform, ethyl acetate, DMF, methylisobutyl ketone, THF and dimethoxy ethane, for example.

Alternatively, the said rearrangement reaction is accomplished in aninactive solvent and in the presence of a base, such as potassiumcarbonate, sodium carbonate, triethylamine and pyridine. The amount ofthe base is in a range of from 0.5 to 2.0 mol based on the total amountof the compounds of formulas (6a) and (6b), and any of THF, dioxane,t-amyl alcohol, t-butyl alcohol and the like can be used as the solvent.Temperature suitable for the reaction is in a range of from an ambienttemperature to a boiling point of the solvent used.

Moreover, by using a base together with a dehydrating and condensatingagent, such as DCC, and without isolating the compounds of formulas (6a)and (6b), the compound of formula (1--1) can be obtained as well. As anexample for the base used in this reaction, potassium carbonate, sodiumcarbonate, triethylamine, pyridine, etc. are given, and the amount ofsuch base is in a range of from 0.5 to 2.0 mol based on the amount ofthe compound of formula (3). In this case, any of THF, dioxane, t-amylalcohol, t-butyl alcohol and the like can be used as the solvent, and itis preferable to proceed the reaction in a temperature range of from anambient temperature to a boiling point of the solvent used.

Whereas, the compound of formula (4) can be also manufactured accordingto the following reaction formula which is described in Chem. Ind.(London), 65 (1960), etc. ##STR7##

In the reaction formula shown above, R¹, R², Q, Z and M are as definedabove, and X is a halogen atom.

In this reaction, the compound of formula (4) is obtained by firstlyreacting a toluene derivative of formula (7) with a halogenating agentto obtain a gem-dihalogenated compound of formula (8), then subsequentlysubjecting it to a reaction with either an alcohol or a mercaptocompound, which are represented by a formula, MZH, wherein M and Z areas defined above, in the presence of an appropriate base.

Manufacturing Method (ii) ##STR8##

In the reaction formula shown above, R¹, R², R⁴, R⁵, Z and M are asdefined above.

As shown in the reaction formula above, an objective compound of formula(1-2) is manufactured by causing hydrolysis of an acetal compound offormula (1) with an acid.

In the reaction described above, as such acid used therein, an inorganicacid, such as hydrochloric acid and sulfuric acid, a Louis acid, such aszinc chloride, titan tetrachloride and p-toluenesulfonic acid, anorganic acid, such as acetic acid and trifluoroacetic acid, can be givenas the examples.

And, as an example for a solvent to be used in this reaction, H₂ O, analcohol, such as methanol and ethanol, a halogenated hydrocarbon, suchas methylene chloride and chloroform, an aromatic hydrocarbon, such asbenzene and toluene, a ketone, such as acetone and methyl ethyl ketone,an ether, such as diethyl ether and THF, acetonitrile, DMF and the likeare given.

The mixture prepared for the reaction is stirred at a temperatureranging from -10° C. to a boiling point of a solvent used, and theproduct obtained from the reaction must be handled according to acustomary method for after-treatment. ##STR9##

In the reaction formula hereinabove, R¹, R³ and Q are as defined above,and R' is a lower alkyl.

A benzoate of formula (11) can be manufactured by firstly subjecting acompound substituted with a chlorine atom at 4th position of its benzenering of formula (9) with a mercapto compound of formula"R'SH", whereinR' is a lower alkyl, in the presence of a base to obtain a compoundsubstituted with SR' at the 4th-position of its benzene ring of formula(10), then oxidizing the compound of formula (10). The compound offormula (10), wherein SO_(n) R', wherein n is 1 or 2, is substituted toa position other than the 4th-position of its benzene ring can beobtained by converting from a compound being substituted with a chlorineatom at the corresponding position.

As an example for the base usable in the reaction described hereinabove,an alkali metal hydroxide, such as sodium hydroxide and potassiumhydroxide, a metal alkoxide, such as sodium methoxide, sodium ethoxideand potassium t-butoxide, a carbonate, such as sodium carbonate andpotassium carbonate, a hydride, such as sodium hydride, an organic base,such as triethylamine, 1,8-diaza-bicyclo 5,4,0!unde-7-cene (DBU) andpyridine, are given. Also, as an example for the solvent used in thereaction, an alcohol, such as methanol and ethanol, an ether, such asTHF and 1,2-dimethoxy ethane, an amide, such as DMF andN,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetonitrile, benzene,toluene, xylene, and the like are given.

The subsequent oxidation reaction is carried out by using an oxidizingagent, for example, a peroxy acid, such as hydrogen peroxide, peraceticacid, perbenzoic acid and m-chloroperbenzoic acid, and a hypochlorousacid, such as sodium hypochloride and potassium hypochloride in an inertsolvent, such as water, an organic acid like acetic acid, an alcoholsuch as methanol or ethanol, a halogenated hydrocarbon like methylenechloride, chloroform or methylene tetrachloride. The reaction mayproceed smoothly at a temperature range of from an ambient temperatureto a boiling point of a solvent used.

An aldehyde compound of formula (c) shown below, which is an importantintermediate for synthesizing the compound according to the presentinvention, can be manufactured pursuant to the following reactionformula. ##STR10##

In the reaction formula shown above, R¹, R² and Q are as defined above,and W is a halogen atom.

As can be seen from the reaction formula as shown above, the aldehydederivative of formula (c) can be manufactured by firstly obtaining abenzylhalide derivative of formula (b) from a toluene derivative offormula (a) according to a publicly-known method, for example, a methodto proceed a reaction with either of a halogen atom, such as chlorineand bromine, or a halogenating agent, such as N-bromosuccineimide (NBS)and N-chlorosuccineimide (NCS), in the presence of either light or aninitiating agent for radical reaction, such as benzoyl peroxide, thenconverting the benzylhalide derivative obtained to the aldehydederivative according to a method described in J. Am. Chem. Soc., 71,1767 (1949). More particularly, the aldehyde derivative can bemanufactured by subjecting the benzylhalide derivative of formula (b) toa reaction with an alkali metal salt of a nitroalkane, such as2-nitropropane, in an alcohol, such as methanol and ethanol, at atemperature in a range of from 0° C. to a boiling point of a solventused.

5-hydroxypyrazoles of formula (3) can be manufactured according to thereaction formula represented hereinbelow, which is disclosed in, forexamples, Japanese Patent Laid-opens No. Sho 62-234069 Gazette or No.Hei 3-44375 Gazette. ##STR11##

The compound of formula (1) according to the present invention may existin various forms of tautomers, such like as illustrated below. All ofthese tautomers shall be included in the scope of the compoundsaccording to the present invention. ##STR12##

When the compound of formula (1) contains a free hydroxyl group, it ispossible to obtain the derivatives from the compound of formula (1),such as the salts thereof, particularly the agriculturally andhorticulturally acceptable salts thereof, enamines or those analogs,acylate, sulfonate, carbamate, ether, thioether, sulfoxide and sulfone.As a proper example for the said agriculturally and horticulturallyacceptable salts, a sodium salt, a potassium salt, a calcium salt and aammonium salt are given.

As an example for the ammonium salt, a salt formed with an ion offormula; N⁺ RaRbRcRd, wherein Ra, Rb, Rc and Rd are each independentlyhydrogen or occasionally a C₁₋₁₀ alkyl substituted by hydroxyl or thelike, is given. If any one of Ra, Rb, Rc and Rd is a substituted-alkylgroup, it is preferable that Ra, Rb, Rc and Rd contain 1-4 carbon atoms,respectively.

Each of the enamines and those analogs described above are a compound ofwhich part of hydroxy group being converted to a group of formula;--NReRf, wherein Re and Rf are each independently hydrogen, anunsubstituted or substituted C₁₋₆ alkyl or an unsubstituted orsubstituted aryl, such as phenyl, a halogen atom, a group of formula;S(O)gRh, wherein Rh is an unsubstituted or substituted C₁₋₆ alkyl or anunsubstituted or substituted aryl, such as phenyl, and g is 0 or aninteger of 1 or 2.

Each of the appropriate acylate, an ether and a carbamate derivativedescribed above, is a compound of which part of hydrogen group beingconverted to a group of formulas; --OCORi, --ORj or --OCONRkRl, whereinRi and Rj are same as Rh as described above, and Rk and Rl are same asRe as described above.

These derivatives described above can be manufactured according to acustomary manufacturing method.

After completing a reaction according to such manufacturing method, itis necessary to take an ordinary after-treatment procedure to obtain thecompound of the present invention. The structural formulas of thecompounds of the present invention were determined based on examinationsconducted by using IR, NMR, MS, etc.

(Herbicide)

The compounds according to the present invention have an excellentherbicidal activity against weeds grown in upland crop fields either bysoil application or foliar application method. In particular, thecompounds of the present invention can demonstrate higher herbicidaleffect on various weeds growing in upland crops, such as giantfox-tails, wild oats, a velvet leaf and pigweed, and some compoundswhich are selectively non-hazardous to maize, cereals, soybean, cotton,etc. are also contained in such compounds of the present invention.

In the compounds of the present invention, compounds which have plantgrowth regulating activity, such as growth retarding activity, againstuseful plants, such as agricultural crops, ornamental plants and fruittrees, are contained as well.

Further, in the compounds of the present invention, compounds which havean excellent herbicidal activity against weeds grown in paddy ricefields, such as barnyardgrass, Cyperus difformis, Sagittaria trifolia,and Scirpus juncoides, and are selectively non-hazardous to rice plants,are also contained.

In addition, the compounds of the present invention can also be appliedfor weed control in orchards, lawns, railways, vacant lands, etc.

Moreover, in the compounds of the present invention, compounds whichhave plant growth regulating activity, fungicidal activity, insecticidalactivity and acaricidal activity, are also contained.

The herbicides according to the present invention comprise one or morecompounds of the present invention as the active ingredient(s). At apractical application of the compounds of the present invention, suchcompounds can be applied as it is without combining with other elements.Alternatively, the compounds of the present invention can be preparedinto a formulation which is normally employed for plant protectionchemicals, such as wettable powder, dust, emulsifiable concentrate,suspension and flowable formulation. As an additive or a filler to beused for a solid-type formulation, vegetable-origin powder, such assoybean powder and wheat flour, mineral fine powder, such asdiatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite andclay, and organic or inorganic materials, such as sodium benzoate, ureaand Glauber's salt, can be used. In case liquid-type formulations arerequired, a petroleum fraction, such as kerosine, xylene and solventnaphtha, cyclohexane, cyclohexanone, DMF, DMSO alcohol, acetone,trichloroethylene, methylisobutyl ketone, mineral oil, vegetable oil,water, etc. can be used as a solvent. In order to assure uniform andstable physico-chemical properties of such formulations, a surfaceactive agent may be used, if appropriate. As an example for the surfaceactive agent, though there is no particular limitation on that, anon-ionic surface active agent, such as an alkylphenyl ether added withpolyoxy ethylene, an alkyl ether added with polyoxy ethylene, a higherfatty acid ester added with polyoxy ethylene, a sorbitan higher fattyacid ester added with polyoxy ethylene and a tristyrylphenyl ether addedwith polyoxy ethylene; a sulfate ester and an alkylbenzenesulfonate ofan alkylphenyl ether added with polyoxy ethylene; a sulfate ester, analkyl sulfate, an alkylnaphthalenesulfonate, a polycarboxylate and aligninsulfonate of a higher alcohol, a formaldehyde condensate of analkyl naphthalene sulfonate, an isobutylene-anhydrous maleic acidco-polymer and the like are given.

The content of an active ingredient in the herbicide according to thepresent invention may differ depending upon formulation types asdescribed above. For example, the content of the active ingredient canbe in a range of from 5 to 90% by weight (hereinafter %), and preferablyfrom 10 to 85%, for a wettable powder formulation; from 3 to 70%, andpreferably from 5 to 60%, for an emulsifiable concentrate formulation;and from 0.01 to 50%, and preferably from 0.05 to 40%, for a granularformulation.

The wettable powder and the emulsifiable concentrate obtained asdescribed above can be applied in a form of suspension or emulsion,respectively, after diluting them with appropriate volume of water. Thegranules obtained as described above can be directly applied to and/orincorporated into soil without dilution prior to or after germination ofweeds. At a practical application of the herbicide according to thepresent invention, an active ingredient in an appropriate amount morethan 0.1 g/ha shall be applied.

The herbicide according to the present invention can be used in mixingwith any of other known fungicides, insecticides, acaricides,herbicides, plant growth regulators, fertilizers, etc. In particular, itis possible to reduce a required dose of the inventive herbicide to usethanks to a mixing with other herbicides. In this case, such mixing mayprovide an effect not only to reduce labours required for weeding butalso to give higher herbicidal performance because of a synergisticaction derived from a herbicide mixed together. Mixing of the inventiveherbicide with a plurality of other known herbicides is also allowable.

As an example for a herbicide to be preferably associated with theinventive herbicide, an anilide herbicide, such as diflufenican andpropanil, a chloroacetoanilide herbicide, such as alachlor andpretilachlor, an aryloxy alkanoic acid herbicide, such as 2,4-D and2,4-DB, an aryloxyphenoxyalkanic acid herbicides, such as diclofopmethyland phenoxaprop-ethyl, an arylcarboxylic acid herbicide, such asdicamba, pyrithiobac, an imidazolinone herbicide, such as imazaquin andimazethapyr, an urea herbicide, such as diuron and isoproturon, acarbamate herbicide, such as chlorprofam and phenmediphame, athiocarbamate herbicide, such as thiobencarb and EPTC, a dinitro anilineherbicide, such as trifluraline and pendimethalin, a diphenyl etherherbicide, such as acifluorfen and fomesafen, a sulfonylurea herbicide,such as bensulfuron-methyl and nicosulfuron, a triazinone herbicide,such as metribuzin and metamitron, a triazine herbicide, such asatrazine and cyanazine, a triazopyrimidine herbicide, such asflumeturam, a nitrile-type herbicide, such as bromoxynil anddichlobenil, a phosphoric acid herbicide, such as glyphosate andglyphosinate, a quaternized ammonium salt herbicide, such as paraquatand difenzoquat, a cyclic imide herbicide, such as flumiclorac-pentyland fluthiacet-methyl, isoxaben, ethofumesate, quinclorac, cromazone,sulcotrione, synmethyline, dithiopyr, pyrazolate, pyridate, flupoxam,bentazon, benflusate, and a cyclohexanedione herbicides, such assethoxydim and tralcoxydim, are given. In addition, a vegetable oil andan oil concentrate may be added to a mixture of the inventive herbicidewith one or more of the herbicides exemplified above.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the present invention is further described in detail with referringto the following Examples and Reference Examples.

EXAMPLE 1 Preparation of1-ethyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoyl)pyrazole(Compound No. 1-2) ##STR13##

To ethyl acetate in a volume of 50 ml, was dissolved2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoic acid in an amount of3.0 g (9.7 mmol), and to the resulting solution, were added DCC in anamount of 2.2 g (10.7 mmol) and 1-ethyl-5-hydroxypyrazole hydrochloridein an amount of 1.4 g (9.7 mmol) while cooling with ice and the mixturewas subsequently stirred for a night at an ambient temperature.Insoluble product precipitated was filtrated, and the filtrate wascondensed under reduce pressure. The residue obtained was then dissolvedin chloroform in a volume of 30 ml, and the resulting solution wasstirred for 6 hours at an ambient temperature following to an additionof acetone cyanohydrin in an amount of 0.25 g (2.9 mmol) andtriethylamine in an amount of 2.0 g (20 mmol) thereto. Thereacted-mixture was washed with 1-N hydrochloric acid and then withsaturated saline solution, dried over anhydrous magnesium sulfate andsubjected to distillation for eliminating the solvent therein. Thecrystals remained were washed with methanol to obtain1-ethyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoyl)pyrazolein an amount of 1.6 g. The melting point of this compound is in a rangeof from 168° to 170° C.

EXAMPLE 2 Preparation of1-methyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-dimethylthiomethylbenzoyl)pyrazole(Compound No. 1-6) ##STR14##

To ethyl acetate in a volume of 20 ml, was dissolved2-chloro-4-methanesulfonyl-3-dimethylthiobenzoic acid in an amount of0.84 g (2.5 mmol), and to the resulting solution, were added DCC in anamount of 0.56 g (2.8 mmol), 1-methyl-5-hydroxypyrazole hydrochloride inan amount of 0.33 g (2.5 mmol) and triethylamine in an amount of 0.25 g(2.5 g (2. 5 mmol) while cooling with ice and the mixture wassubsequently stirred for a night at an ambient temperature. Insolubleproduct precipitated was filtrated, and the filtrate was condensed underreduce pressure. The residue obtained was then dissolved in chloroformin a volume of 10 ml, and the resulting solution was stirred for a nightat an ambient temperature following to an addition of acetonecyanohydrin in an amount of 0.06 g (0.7 mmol) and triethylamine in anamount of 0.5 g (5 mmol) thereto. The reacted-mixture was washed with1-N hydrochloric acid and then with saturated saline solution, driedover anhydrous magnesium sulfate and subjected to distillation foreliminating the solvent therein. The crystals remained were washed withmethanol to obtain1-methyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-dimethylthiomethylbenzoyl)pyrazole in an amount of 0.26 g. The melting point of this compound isin a range of from 215° to 217° C.

EXAMPLE 3 Preparation of1-methyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-formylbenzoyl)pyrazole(Compound No. 2-1) ##STR15##

To acetone in a volume of 40 ml, was dissolved1-methyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoyl)pyrazole in an amount of 1.8 g (4.7 mmol), andhydrochloric acid in an amount of 2 ml was then added to the resultingsolution. The mixture was stirred for 1 hour under heating reflux, andthe solvent therein was removed by distillation. Crystals precipitatedwas washed with ether to obtain1-methyl-5-hydroxy-4-(2-chloro-4-methanesulfonyl-3-formylbenzoyl)pyrazolein an amount of 1.5 g. The melting point of this compound is in a rangeof from 140° to 142° C.

Now, examples for preparing intermediates which are important for thecompounds according to the present invention are described hereinbelowas reference.

Reference Example 1 Preparation of methyl 2,4-dichloro-3-formyl benzoate##STR16##

To methanol in a volume of 100 ml, was added 28% methanol solution ofsodium methylate in an amount of 26.61 g, and to the resulting solution,was fed dropwise 2-nitro propane in an amount of 12.29 g while coolingwith ice to a temperature lower than 25° C. The mixture was then addedwith methyl 3-bromomethyl-2,4-dichlorobenzoate in an amount of 41.16 gand stirred for 30 minutes under heating reflux. After completingreaction, the reacted-mixture was cooled and condensed under reducedpressure. A residue obtained was then dissolved in ethyl acetate in avolume of 1,000 ml, and the resulting solution was then washed with 1%aqueous solution of sodium hydroxide while cooling with ice. An organiclayer resulted was washed with water and then with saturated salinesolution, and was dried over anhydrous magnesium sulfate. Crystals,which were obtained after condensation of the organic layer under reducepressure, were washed with benzene and then with n-hexane to obtain anobjective compound of methyl 2,4-dichloro-3-formylbenzoate in an amountof 22.0 g in crystalline state. The melting point of this compound is ina range of from 103° to 104° C.

Reference Example 2 Preparation of 2,4-dichloro-3-formylbenzoic acid##STR17##

Methyl 2,4-dichloro-3-formyl benzoate in an amount of 1.04 g wasdissolved in ethanol in an amount of 5 ml, and the resulting solutionwas then added with 1-N solution of sodium hydroxide in an amount of 10ml and subsequently stirred for 17 hours at an ambient temperature. Thereacted-solution was then poured into ice water in a volume of 40 ml,and the mixture was adjusted with concentrated sulfuric acid to acidiccondition. Crystals precipitated were filtrated and dried to obtain anobjective compound of 2,4-dichloro-3-formylbenzoic acid in an amount of0.75 g in crystalline state. The melting point of this compound is in arange of from 188° to 190° C.

Reference Example 3 Preparation of methyl2-chloro-4-methanesulfonyl-3-dimethoxymethyl benzoate ##STR18##

Methyl 2-chloro-4-methanesulfonyl-3-formyl benzoate in an amount of 3.0g (11 mmol) was dissolved in methanol in a volume of 50 ml, and theresulting solution was then added with concentrated sulfuric acid in anamount of 0.5 g and subsequently stirred for 8 hours under heatingreflux. After condensing solvent in the mixture under reduced pressure,a residue obtained was dissolved in benzene, washed with 3% aqueoussolution of sodium hydrogencarbonate and then with saturated salinesolution and further dried over anhydrous magnesium sulfate. Aftercondensing the solvent and then purifying the condensate with silica gelcolumn chromatography for obtaining the objective compound in an amountof 3.0 g.

¹ H-NMR (δppm, CDCL₃): 3.24(3H, s), 3.54(6H, s), 3.98(3H, s), 6.28(1H,s), 7.70(1H, d), 8.19(1H, d)

Reference Example 4 Preparation of2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoic acid ##STR19##

Methyl 2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoate in an amountof 3.0 g (9.3 mmol) was dissolved in methanol in a volume of 30 ml, andto the resulting solution, was added 10% aqueous solution of sodiumhydroxide in a volume of 20 ml, and then, the mixture was stirred for 1hour at an ambient temperature. The reacted-mixture was then added with1-N hydrochloric acid to make it acidic, and crystals precipitated werefiltrated, washed with water and dried to obtain the objective compoundin an amount of 2.5 g.

¹ H-NMR(δppm, CDCl₃): 2.99(3H, s), 3.56(6H, s), 6.29(1H, s), 7.89(1H,d), 8.24(1H, d)

Reference Example 5 Preparation of methyl2-chloro-4-methanesulfonyl-3-dimethylthiomethylbenzoate ##STR20##

Methyl 2-chloro-4-methanesulfonyl-3-formylbenzoate in an amount of 1.5 g(5.4 mmol) was dissolved in methylene chloride in a volume of 15 ml, andto the resulting solution, methylmercaptan in an amount of 0.65 g (14mmol) was gradually blown under a temperature of 10° C. Then, aluminiumchloride in an amount of 0.22 g (1.7 mmol) was gradually added to themixture at 10° C. and was stirred for 3 hours at an ambient temperature.The reacted-mixture was washed with water and dried over anhydrousmagnesium sulfate, and following to condensating solvent therein underreduced pressure, the objective compound in an amount of 1.8 g wasobtained.

¹ H-NMR(δppm, CDCl₃): 2.37(6H, s), 3.24(3H, s), 3.98(3H, s), 6.22(1H,s), 7.66(1H, d). 8.10(1H, d)

Reference Example 6 Preparation of2-chloro-4-methanesulfonyl-3-dimethylthiomethylbenzoic acid ##STR21##

Methyl 2-chloro-4-methanesulfonyl-3-dimethlthiomethylbenzoate in anamount of 1.80 g (5.08 mmol) was dissolved in methanol in a volume of 10ml, and to the resulting solution, was added 10% aqueous solution ofsodium hydroxide in a volume of 10 ml, and then, the mixture was stirredfor 8 hour at an ambient temperature. The reacted-mixture was then addedwith 1-N hydrochloric acid to make it acidic, and crystals precipitatedwere filtrated, washed with water and dried to obtain the objectivecompound in an amount of 1.69 g.

¹ H-NMR(δppm, CDCl₃): 2.33(6H, s), 3. 22(3H, s), 6.21(1H, s), 7.68(1H,d), 8.04(1H, d)

Now, the representative examples for the compounds according to thepresent invention including the compounds prepared in the examplesdescribed above are represented in Tables 1 and 2.

                                      TABLE 1                                     __________________________________________________________________________     ##STR22##                                                                    Compound                              Physical Data                           No.   R.sup.1                                                                            R.sup.2                                                                            R.sup.4  R.sup.5   ZM   ! Melting Point                       __________________________________________________________________________                                          °C.                              1-1   2-Cl 4-SO.sub.2 Me                                                                      Me       H         OMe                                                                               157-159!                               1-2   2-Cl 4-SO.sub.2 Me                                                                      Et       H         OMe                                                                               168-170!                               1-3   2-Cl 4-SO.sub.2 Me                                                                      Me       Me        OMe                                                                               235-237!                               1-4   2-Cl 4-SO.sub.2 Me                                                                      Me       H         OEt                                                                              amorphous NMR-1                         1-5   2-Cl 4-SO.sub.2 Me                                                                      Et       H         OEt                                                                              amorphous NMR-2                         1-6   2-Cl 4-SO.sub.2 Me                                                                      Me       H         SMe                                                                               215-217!                               1-7   2-Cl 4-SO.sub.2 Me                                                                      Et       H         SMe                                                                               183-185!                               1-8   2-CH.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       H         OMe                                                                               164-167!                               1-9   2-CH.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       H         OMe                                                                               148-150!                               1-10  2-Cl 4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-11  2-Cl 4-SO.sub.2 Me                                                                      Me       Et        OMe                                        1-12  2-Cl 4-SO.sub.2 Me                                                                      Me       Et        SMe                                        1-13  2-Cl 4-SO.sub.2 Me                                                                      Me       CHCH.sub.2                                                                              OMe                                        1-14  2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-15  2-Cl 4-SO.sub.2 Me                                                                      Me       C CH      OMe                                        1-16  2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           OMe                                        1-17  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             OMe                                        1-18  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclohexyl                                                                              OMe                                        1-19  2-Cl 4-SO.sub.2 Me                                                                      Me       CF.sub.3  OMe                                        1-20  2-Cl 4-SO.sub.2 Me                                                                      Me       CHCH.sub.2                                                                              SMe                                        1-21  2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-22  2-Cl 4-SO.sub.2 Me                                                                      Me       C CH      SMe                                        1-23  2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           SMe                                        1-24  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             SMe                                        1-25  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclohexyl                                                                              SMe                                        1-26  2-Cl 4-SO.sub.2 Me                                                                      Me       CF.sub.3  SMe                                        1-27  2-Cl 4-Cl Me       CHCH.sub.2                                                                              OMe                                        1-28  2-Cl 4-Cl Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-29  2-Cl 4-Cl Me       C CH      OMe                                        1-30  2-Cl 4-Cl Me       CH.sub.2 C CH                                                                           OMe                                        1-31  2-Cl 4-Cl Me       cyclopropyl                                                                             OMe                                        1-32  2-Cl 4-Cl Me       cyclohexyl                                                                              OMe                                        1-33  2-Cl 4-Cl Me       CF.sub.3  OMe                                        1-34  2-Cl 4-Cl Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-35  2-Cl 4-Cl Me       CH.sub.2 C CH                                                                           SMe                                        1-36  2-Cl 4-Cl Me       cyclopropyl                                                                             SMe                                        1-37  2-Cl 4-Cl Me       CF.sub.3  SMe                                        1-38  2-Me 4-SO.sub.2 Me                                                                      Me       Me        OMe                                        1-39  2-Me 4-SO.sub.2 Me                                                                      Me       Et        OMe                                        1-40  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-41  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           OMe                                        1-42  2-Me 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             OMe                                        1-43  2-Me 4-SO.sub.2 Me                                                                      Me       CF.sub.3  OMe                                        1-44  2-Me 4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-45  2-Me 4-SO.sub.2 Me                                                                      Me       Et        SMe                                        1-46  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-47  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           SMe                                        1-48  2-Me 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             SMe                                        1-49  2-Me 4-SO.sub.2 Me                                                                      Me       CF.sub.3  SMe                                        1-50  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       H         OMe                                        1-51  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       Me        OMe                                        1-52  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-53  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           OMe                                        1-54  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             OMe                                        1-55  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CF.sub.3  OMe                                        1-56  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       H         SMe                                        1-57  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-58  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-59  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           SMe                                        1-60  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             SMe                                        1-61  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CF.sub.3  SMe                                        1-62  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       H         OMe                                        1-63  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       Me        OMe                                        1-64  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-65  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           OMe                                        1-66  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             OMe                                        1-67  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CF.sub.3  OMe                                        1-68  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       H         SMe                                        1-69  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-70  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-71  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           SMe                                        1-72  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             SMe                                        1-73  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CF.sub.3  SMe                                        1-74  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       H         OMe                                        1-75  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       Me        OMe                                        1-76  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-77  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           OMe                                        1-78  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             OMe                                        1-79  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CF.sub.3  OMe                                        1-80  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       H         SMe                                        1-81  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-82  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-83  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 C CH                                                                           SMe                                        1-84  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       cyclopropyl                                                                             SMe                                        1-85  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CF.sub.3  SMe                                        1-86  2-Cl 4-Cl Et       CHCH.sub.2                                                                              OMe                                        1-87  2-Cl 4-Cl Et       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-88  2-Cl 4-Cl Et       C CH      OMe                                        1-89  2-Cl 4-Cl Et       CH.sub.2 C CH                                                                           OMe                                        1-90  2-Cl 4-Cl Et       cyclopropyl                                                                             OMe                                        1-91  2-Cl 4-Cl Et       cyclohexyl                                                                              OMe                                        1-92  2-Cl 4-Cl Et       CF.sub.3  OMe                                        1-93  2-Cl 4-Cl Et       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-94  2-Cl 4-Cl Et       CH.sub.2 C CH                                                                           SMe                                        1-95  2-Cl 4-Cl Et       cyclopropyl                                                                             SMe                                        1-96  2-Cl 4-Cl Et       CF.sub.3  SMe                                        1-97  2-Me 4-SO.sub.2 Me                                                                      Et       Me        OMe                                        1-98  2-Me 4-SO.sub.2 Me                                                                      Et       Et        OMe                                        1-99  2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-100 2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           OMe                                        1-101 2-Me 4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             OMe                                        1-102 2-Me 4-SO.sub.2 Me                                                                      Et       CF.sub.3  OMe                                        1-103 2-Me 4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-104 2-Me 4-SO.sub.2 Me                                                                      Et       Et        SMe                                        1-105 2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-106 2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           SMe                                        1-107 2-Me 4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             SMe                                        1-108 2-Me 4-SO.sub.2 Me                                                                      Et       CF.sub.3  SMe                                        1-109 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       H         OMe                                        1-110 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       Me        OMe                                        1-111 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-112 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           OMe                                        1-113 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             OMe                                        1-114 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CF.sub.3  OMe                                        1-115 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       H         SMe                                        1-116 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-117 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-118 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           SMe                                        1-119 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             SMe                                        1-120 2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CF.sub.3  SMe                                        1-121 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       H         OMe                                        1-122 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       Me        OMe                                        1-123 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-124 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           OMe                                        1-125 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             OMe                                        1-126 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CF.sub.3  OMe                                        1-127 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       H         SMe                                        1-128 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-129 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-130 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           SMe                                        1-131 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             SMe                                        1-132 2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CF.sub.3  SMe                                        1-133 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       H         OMe                                        1-134 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       Me        OMe                                        1-135 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     OMe                                        1-136 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           OMe                                        1-137 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             OMe                                        1-138 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CF.sub.3  OMe                                        1-139 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       H         SMe                                        1-140 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-141 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                                                     SMe                                        1-142 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 C CH                                                                           SMe                                        1-143 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       cyclopropyl                                                                             SMe                                        1-144 2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CF.sub.3  SMe                                        1-145 2-Cl 4-SMe                                                                              Me       H         OMe                                        1-146 2-Cl 4-SMe                                                                              Et       H         OMe                                        1-147 2-Cl 4-SMe                                                                              Me       Me        SMe                                        1-148 2-Cl 4-SMe                                                                              Et       Me        SMe                                        1-149 2-Cl 4-SOMe                                                                             Me       H         OMe                                        1-150 2-Cl 4-SOMe                                                                             Et       H         OMe                                        1-151 2-Cl 4-SOMe                                                                             Me       Me        SMe                                        1-152 2-Cl 4-SOMe                                                                             Et       Me        SMe                                        1-153 2-F  4-SO.sub.2 Me                                                                      Me       H         OMe                                        1-154 2-F  4-SO.sub.2 Me                                                                      Et       H         OMe                                        1-155 2-F  4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-156 2-F  4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-157 2-Br 4-SO.sub.2 Me                                                                      Me       H         OMe                                        1-158 2-Br 4-SO.sub.2 Me                                                                      Et       H         OMe                                        1-159 2-Br 4-SO.sub.2 Me                                                                      Me       Me        SMe                                        1-160 2-Br 4-SO.sub.2 Me                                                                      Et       Me        SMe                                        1-161 2-Cl 4-SO.sub.2 Me                                                                      H        H         OMe                                        1-162 2-Cl 4-SO.sub.2 Me                                                                      H        H         SMe                                        1-163 2-Cl 4-SO.sub.2 Me                                                                      H        Me        OMe                                        1-164 2-SO.sub.2 Me                                                                      4-Cl H        H         OMe                                        1-165 2-SO.sub.2 Me                                                                      4-Cl Me       H         OMe                                        1-166 2-SO.sub.2 Me                                                                      4-Cl CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-167 2-SO.sub.2 Me                                                                      4-Cl CH.sub.2 C CH                                                                          H         OMe                                        1-168 2-SO.sub.2 Me                                                                      4-Cl cyclopropyl                                                                            H         OMe                                        1-169 2-SO.sub.2 Me                                                                      4-Cl CF.sub.3 H         OMe                                        1-170 2-SO.sub.2 Me                                                                      4-Me H        H         OMe                                        1-171 2-SO.sub.2 Me                                                                      4-Me Me       H         OMe                                        1-172 2-SO.sub.2 Me                                                                      4-Me CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-173 2-SO.sub.2 Me                                                                      4-Me CH.sub.2 C CH                                                                          H         OMe                                        1-174 2-SO.sub.2 Me                                                                      4-Me cyclopropyl                                                                            H         OMe                                        1-175 2-SO.sub.2 Me                                                                      4-Me CF.sub.3 H         OMe                                        1-176 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         Me       H         OMe                                        1-177 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-178 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CH.sub.2 C CH                                                                          H         OMe                                        1-179 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         cyclopropyl                                                                            H         OMe                                        1-180 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CF.sub.3 H         OMe                                        1-181 2-SO.sub.2 Me                                                                      4-OMe                                                                              Me       H         OMe                                        1-182 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-183 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 C CH                                                                          H         OMe                                        1-184 2-SO.sub.2 Me                                                                      4-OMe                                                                              cyclopropyl                                                                            H         OMe                                        1-185 2-SO.sub.2 Me                                                                      4-OMe                                                                              CF.sub.3 H         OMe                                        1-186 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        Me       H         OMe                                        1-187 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-188 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CH.sub.2 C CH                                                                          H         OMe                                        1-189 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        cyclopropyl                                                                            H         OMe                                        1-190 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CF.sub.3 H         OMe                                        1-191 2-SMe                                                                              4-Cl Et       H         OMe                                        1-192 2-SOMe                                                                             4-Cl Et       H         OMe                                        1-193 2-Cl 5-SO.sub.2 Me                                                                      Me       H         OMe                                        1-194 2-Cl 6-SO.sub.2 Me                                                                      Me       H         OMe                                        1-195 4-Cl 5-SO.sub.2 Me                                                                      Me       H         OMe                                        1-196 4-Cl 6-SO.sub.2 Me                                                                      Me       H         OMe                                        1-197 2-Cl 4-SO.sub.2 Me                                                                      Me       H         OEt                                        1-198 2-Cl 4-SO.sub.2 Me                                                                      Me       H         SEt                                        1-199 2-Cl 4-SO.sub.2 Me                                                                      Me       H         OPr.sup.i                                  1-200 2-Cl 4-SO.sub.2 Me                                                                      Me       H         SPr.sup.i                                  1-201 2-Cl 4-SO.sub.2 Me                                                                      Me       H         OBu                                        1-202 2-Cl 4-SO.sub.2 Me                                                                      Me       H         SBu                                        1-203 2-NO.sub.2                                                                         4-Cl Me       H         OMe                                        1-204 2-NO.sub.2                                                                         4-Cl CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-205 2-NO.sub.2                                                                         4-Cl CH.sub.2 C CH                                                                          H         OMe                                        1-206 2-NO.sub.2                                                                         4-Cl cyclopropyl                                                                            H         OMe                                        1-207 2-NO.sub.2                                                                         4-Cl CF.sub.3 H         OMe                                        1-208 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      Me       H         OMe                                        1-209 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-210 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CH.sub.2 C CH                                                                          H         OMe                                        1-211 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      cyclopropyl                                                                            H         OMe                                        1-212 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CF.sub.3 H         OMe                                        1-213 2-NO.sub.2                                                                         4-Cl Me       H         SMe                                        1-214 2-NO.sub.2                                                                         4-Cl CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-215 2-NO.sub.2                                                                         4-Cl CH.sub.2 C CH                                                                          H         SMe                                        1-216 2-NO.sub.2                                                                         4-Cl cyclopropyl                                                                            H         SMe                                        1-217 2-NO.sub.2                                                                         4-Cl CF.sub.3 H         SMe                                        1-218 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      Me       H         SMe                                        1-219 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-220 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CH.sub.2 C CH                                                                          H         SMe                                        1-221 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      cyclopropyl                                                                            H         SMe                                        1-222 2-NO.sub.2                                                                         2-SO.sub.2 Me                                                                      CF.sub.3 H         SMe                                        1-228 2-Cl 4-SO.sub.2 Me                                                                      .sup.i Pr                                                                              H         SMe                                        1-229 2-Cl 4-SO.sub.2 Me                                                                      Bu       H         SMe                                        1-230 2-Cl 4-SO.sub.2 Me                                                                      .sup.i Pr                                                                              H         SMe                                        1-231 2-Cl 4-SO.sub.2 Me                                                                      Bu       H         SMe                                        1-232 2-CN 4-Cl Me       H         OMe                                        1-233 2-CN 4-Cl CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-234 2-CN 4-Cl CH.sub.2 C CH                                                                          H         OMe                                        1-235 2-CN 4-Cl cyclopropyl                                                                            H         OMe                                        1-236 2-CN 4-Cl CF.sub.3 H         OMe                                        1-237 2-CN 2-SO.sub.2 Me                                                                      Me       H         OMe                                        1-238 2-CN 2-SO.sub.2 Me                                                                      CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-239 2-CN 2-SO.sub.2 Me                                                                      CH.sub.2 C CH                                                                          H         OMe                                        1-240 2-CN 2-SO.sub.2 Me                                                                      cyclopropyl                                                                            H         OMe                                        1-241 2-CN 2-SO.sub.2 Me                                                                      CF.sub.3 H         OMe                                        1-242 2-CN 4-CF.sub.3                                                                         Me       H         OMe                                        1-243 2-CN 4-CF.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-244 2-CN 4-CF.sub.3                                                                         CH.sub.2 C CH                                                                          H         OMe                                        1-245 2-CN 4-CF.sub.3                                                                         cyclopropyl                                                                            H         OMe                                        1-246 2-CN 4-CF.sub.3                                                                         CF.sub.3 H         OMe                                        1-247 2-CF.sub.3                                                                         4-CN Me       H         OMe                                        1-248 2-CF.sub.3                                                                         4-CN CH.sub.2 CHCH.sub.2                                                                    H         OMe                                        1-249 2-CF.sub.3                                                                         4-CN CH.sub.2 C CH                                                                          H         OMe                                        1-250 2-CF.sub.3                                                                         2-CN cyclopropyl                                                                            H         OMe                                        1-251 2-CF.sub.3                                                                         2-CN CF.sub.3 H         OMe                                        1-252 2-CN 4-Cl Me       H         SMe                                        1-253 2-CN 4-Cl CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-254 2-CN 4-Cl CH.sub.2 C CH                                                                          H         SMe                                        1-255 2-CN 4-Cl cyclopropyl                                                                            H         SMe                                        1-256 2-CN 4-Cl CF.sub.3 H         SMe                                        1-257 2-CN 2-SO.sub.2 Me                                                                      Me       H         SMe                                        1-258 2-CN 2-SO.sub.2 Me                                                                      CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-259 2-CN 2-SO.sub.2 Me                                                                      CH.sub.2 C CH                                                                          H         SMe                                        1-260 2-CN 2-SO.sub.2 Me                                                                      cyclopropyl                                                                            H         SMe                                        1-261 2-CN 2-SO.sub.2 Me                                                                      CF.sub.3 H         SMe                                        1-262 2-CN 4-CF.sub.3                                                                         Me       H         SMe                                        1-263 2-CN 4-CF.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-264 2-CN 4-CF.sub.3                                                                         CH.sub.2 C CH                                                                          H         SMe                                        1-265 2-CN 4-CF.sub.3                                                                         cyclopropyl                                                                            H         SMe                                        1-266 2-CN 4-CF.sub.3                                                                         CF.sub.3 H         SMe                                        1-267 2-CF.sub.3                                                                         4-CN Me       H         SMe                                        1-268 2-CF.sub.3                                                                         4-CN CH.sub.2 CHCH.sub.2                                                                    H         SMe                                        1-269 2-CF.sub.3                                                                         4-CN CH.sub.2 C CH                                                                          H         SMe                                        1-270 2-CF.sub.3                                                                         4-CN cyclopropyl                                                                            H         SMe                                        1-271 2-CF.sub.3                                                                         4-CN CF.sub.3 H         SMe                                        1-272 2-CF.sub.3                                                                         4-CF.sub.3                                                                         Me       H         OMe                                        1-273 2-CF.sub.3                                                                         4-CF.sub.3                                                                         Et       H         OMe                                        1-274 2-CF.sub.3                                                                         4-CF.sub.3                                                                         Me       H         SMe                                        1-275 2-CF.sub.3                                                                         4-CF.sub.3                                                                         Et       H         SMe                                        __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR23##                                                                    Compound                          Physical Data                               No.   R.sup.1                                                                            R.sup.2                                                                            R.sup.4  R.sup.5    !Melting Point °C.                 __________________________________________________________________________    2-1   2-Cl 4-SO.sub.2 Me                                                                      Me       H         140-142!                                   2-2   2-Cl 4-SO.sub.2 Me                                                                      Et       H         202-204!                                   2-3   2-Cl 4-SO.sub.2 Me                                                                      Me       Me        174-178!                                   2-4   2-Cl 4-SO.sub.2 Me                                                                      Me       H                                                    2-5   2-Cl 4-SO.sub.2 Me                                                                      Et       H                                                    2-6   2-Cl 4-SO.sub.2 Me                                                                      Me       CHCH.sub.2                                           2-7   2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                  2-8   2-Cl 4-SO.sub.2 Me                                                                      Me       CCH                                                  2-9   2-Cl 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CCH                                         2-10  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                          2-11  2-Cl 4-SO.sub.2 Me                                                                      Me       cyclohexyl                                           2-12  2-Cl 4-SO.sub.2 Me                                                                      Me       CF.sub.3                                             2-13  2-Cl 4-Cl Me       H                                                    2-14  2-Cl 4-Cl Me       Me                                                   2-15  2-Cl 4-Cl Me       CHCH.sub.2                                           2-16  2-Cl 4-Cl Me       CH.sub.2 CHCH.sub.2                                  2-17  2-Cl 4-Cl Me       CCH                                                  2-18  2-Cl 4-Cl Me       CH.sub.2 CCH                                         2-19  2-Cl 4-Cl Me       cyclopropyl                                          2-20  2-Cl 4-Cl Me       cyclohexyl                                           2-21  2-Cl 4-Cl Me       CF.sub.3                                             2-22  2-Me 4-SO.sub.2 Me                                                                      Me       H         185-187!                                   2-23  2-Me 4-SO.sub.2 Me                                                                      Me       CHCH.sub.2                                           2-24  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                  2-25  2-Me 4-SO.sub.2 Me                                                                      Me       CCH                                                  2-26  2-Me 4-SO.sub.2 Me                                                                      Me       CH.sub.2 CCH                                         2-27  2-Me 4-SO.sub.2 Me                                                                      Me       cyclopropyl                                          2-28  2-Me 4-SO.sub.2 Me                                                                      Me       cyclohexyl                                           2-29  2-Me 4-SO.sub.2 Me                                                                      Me       CF.sub.3                                             2-30  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       H                                                    2-31  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       Me                                                   2-32  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                  2-33  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CH.sub.2 CCH                                         2-34  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       cyclopropyl                                          2-35  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Me       CF.sub.3                                             2-36  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       H                                                    2-37  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       Me                                                   2-38  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                  2-39  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CH.sub.2 CCH                                         2-40  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       cyclopropyl                                          2-41  2-OMe                                                                              4-SO.sub.2 Me                                                                      Me       CF.sub.3                                             2-42  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       H                                                    2-43  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       Me                                                   2-44  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 CHCH.sub.2                                  2-45  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CH.sub.2 CCH                                         2-46  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       cyclopropyl                                          2-47  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Me       CF.sub.3                                             2-48  2-Cl 4-SO.sub.2 Me                                                                      Et       CHCH.sub.2                                           2-49  2-Cl 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                  2-50  2-Cl 4-SO.sub.2 Me                                                                      Et       CCH                                                  2-51  2-Cl 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CCH                                         2-52  2-Cl 4-SO.sub.2 Me                                                                      Et       cyclopropyl                                          2-53  2-Cl 4-SO.sub.2 Me                                                                      Et       cyclohexyl                                           2-54  2-Cl 4-SO.sub.2 Me                                                                      Et       CF.sub.3                                             2-55  2-Cl 4-Cl Et       H                                                    2-56  2-Cl 4-Cl Et       Me                                                   2-57  2-Cl 4-Cl Et       CHCH.sub.2                                           2-58  2-Cl 4-Cl Et       CH.sub.2 CHCH.sub.2                                  2-59  2-Cl 4-Cl Et       CCH                                                  2-60  2-Cl 4-Cl Et       CH.sub.2 CCH                                         2-61  2-Cl 4-Cl Et       cyclopropyl                                          2-62  2-Cl 4-Cl Et       cyclohexyl                                           2-63  2-Cl 4-Cl Et       CF.sub.3                                             2-64  2-Me 4-SO.sub.2 Me                                                                      Et       H         211-213!                                   2-65  2-Me 4-SO.sub.2 Me                                                                      Et       CHCH.sub.2                                           2-66  2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                  2-67  2-Me 4-SO.sub.2 Me                                                                      Et       CCH                                                  2-68  2-Me 4-SO.sub.2 Me                                                                      Et       CH.sub.2 CCH                                         2-69  2-Me 4-SO.sub.2 Me                                                                      Et       cyclopropyl                                          2-70  2-Me 4-SO.sub.2 Me                                                                      Et       cyclohexyl                                           2-71  2-Me 4-SO.sub.2 Me                                                                      Et       CF.sub.3                                             2-72  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       H                                                    2-73  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       Me                                                   2-74  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                  2-75  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CH.sub.2 CCH                                         2-76  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       cyclopropyl                                          2-77  2-CF.sub.3                                                                         4-SO.sub.2 Me                                                                      Et       CF.sub.3                                             2-78  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       H                                                    2-79  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       Me                                                   2-80  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                  2-81  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CH.sub.2 CCH                                         2-82  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       cyclopropyl                                          2-83  2-OMe                                                                              4-SO.sub.2 Me                                                                      Et       CF.sub.3                                             2-84  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       H                                                    2-85  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       Me                                                   2-86  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 CHCH.sub.2                                  2-87  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CH.sub.2 CCH                                         2-88  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       cyclopropyl                                          2-89  2-OCF.sub.3                                                                        4-SO.sub.2 Me                                                                      Et       CF.sub.3                                             2-90  2-Cl 4-SMe                                                                              Me       H                                                    2-91  2-Cl 4-SMe                                                                              Et       H                                                    2-92  2-Cl 4-SMe                                                                              Me       Me                                                   2-93  2-Cl 4-SMe                                                                              Et       Me                                                   2-94  2-Cl 4-SOMe                                                                             Me       H                                                    2-95  2-Cl 4-SOMe                                                                             Et       H                                                    2-96  2-Cl 4-SOMe                                                                             Me       Me                                                   2-97  2-Cl 4-SOMe                                                                             Et       Me                                                   2-98  2-F  4-SO.sub.2 Me                                                                      Me       H                                                    2-99  2-F  4-SO.sub.2 Me                                                                      Et       H                                                    2-100 2-F  4-SO.sub.2 Me                                                                      Me       Me                                                   2-101 2-F  4-SO.sub.2 Me                                                                      Et       Me                                                   2-102 2-Br 4-SO.sub.2 Me                                                                      Me       H                                                    2-103 2-Br 4-SO.sub.2 Me                                                                      Et       H                                                    2-104 2-Br 4-SO.sub.2 Me                                                                      Me       Me                                                   2-105 2-Br 4-SO.sub.2 Me                                                                      Et       Me                                                   2-106 2-Cl 4-SO.sub.2 Et                                                                      Me       H                                                    2-107 2-Cl 4-SO.sub.2 Et                                                                      Et       H                                                    2-108 2-Cl 4-SO.sub.2 Et                                                                      Me       Me                                                   2-109 2-Cl 4-SO.sub.2 Et                                                                      Et       Me                                                   2-110 2-SO.sub.2 Me                                                                      4-Cl H        H                                                    2-111 2-SO.sub.2 Me                                                                      4-Cl Me       H                                                    2-112 2-SO.sub.2 Me                                                                      4-Cl Et       H                                                    2-113 2-SO.sub.2 Me                                                                      4-Cl CH.sub.2 CHCH.sub.2                                                                    H                                                    2-114 2-SO.sub.2 Me                                                                      4-Cl CH.sub.2 CCH                                                                           H                                                    2-115 2-SO.sub.2 Me                                                                      4-Cl cyclopropyl                                                                            H                                                    2-116 2-SO.sub.2 Me                                                                      4-Cl CF.sub.3 H                                                    2-117 2-SO.sub.2 Me                                                                      4-Me Me       H                                                    2-118 2-SO.sub.2 Me                                                                      4-Me Et       H                                                    2-119 2-SO.sub.2 Me                                                                      4-Me CH.sub.2 CHCH.sub.2                                                                    H                                                    2-120 2-SO.sub.2 Me                                                                      4-Me CH.sub.2 CCH                                                                           H                                                    2-121 2-SO.sub.2 Me                                                                      4-Me cyclopropyl                                                                            H                                                    2-122 2-SO.sub.2 Me                                                                      4-Me CF.sub.3 H                                                    2-123 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         Me       H                                                    2-124 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         Et       H                                                    2-125 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CH.sub.2 CHCH.sub.2                                                                    H                                                    2-126 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CH.sub.2 CCH                                                                           H                                                    2-127 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         cyclopropyl                                                                            H                                                    2-128 2-SO.sub.2 Me                                                                      4-CF.sub.3                                                                         CF.sub.3 H                                                    2-129 2-SO.sub.2 Me                                                                      4-OMe                                                                              Me       H                                                    2-130 2-SO.sub.2 Me                                                                      4-OMe                                                                              Et       H                                                    2-131 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 CHCH.sub.2                                                                    H                                                    2-132 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 CCH                                                                           H                                                    2-133 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 CHCH.sub.2                                                                    H                                                    2-134 2-SO.sub.2 Me                                                                      4-OMe                                                                              CH.sub.2 CCH                                                                           H                                                    2-135 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        Me       H                                                    2-136 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        Et       H                                                    2-137 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CH.sub.2 CHCH.sub.2                                                                    H                                                    2-138 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CH.sub.2 CCH                                                                           H                                                    2-139 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        cyclopropyl                                                                            H                                                    2-140 2-SO.sub.2 Me                                                                      4-OCF.sub.3                                                                        CF.sub.3 H                                                    2-141 2-SMe                                                                              4-Cl Me       H                                                    2-142 2-SMe                                                                              4-Cl Me       Me                                                   2-143 2-SMe                                                                              4-Cl Et       H                                                    2-144 2-SOMe                                                                             4-Cl Me       H                                                    2-145 2-SOMe                                                                             4-Cl Et       H                                                    2-146 2-NO.sub.2                                                                         4-Cl Me       H                                                    2-147 2-NO.sub.2                                                                         4-Cl Et       H                                                    2-148 2-NO.sub.2                                                                         4-SO.sub.2 Me                                                                      Me       H                                                    2-149 2-NO.sub.2                                                                         4-SO.sub.2 Me                                                                      Et       H                                                    2-150 2-Cl 4-NO.sub.2                                                                         Me       H                                                    2-151 2-Cl 4-NO.sub.2                                                                         Et       H                                                    2-152 2-Cl 4-NO.sub.2                                                                         Me       Me                                                   2-153 2-CN 4-Cl Me       H                                                    2-154 2-CN 4-Cl Et       H                                                    2-155 2-CN 4-SO.sub.2 Me                                                                      Me       H                                                    2-156 2-CN 4-SO.sub.2 Me                                                                      Et       H                                                    2-157 2-Cl 4-CN Me       H                                                    2-158 2-Cl 4-CN Et       H                                                    2-159 2-Cl 4-CN Et       H                                                    2-160 2-CF.sub.3                                                                         4-CN Me       H                                                    2-161 2-CF.sub.3                                                                         4-CN Et       H                                                    2-162 2-CF.sub.3                                                                         4-CN Me       Me                                                   2-163 2-CN 4-SO.sub.2 Me                                                                      CH.sub.2 CHCH.sub.2                                                                    H                                                    2-164 2-CN 4-SO.sub.2 Me                                                                      CH.sub.2 CCH                                                                           H                                                    2-165 2-CN 4-SO.sub.2 Me                                                                      cyclopropyl                                                                            H                                                    2-166 2-CN 4-SO.sub.2 Me                                                                      CF.sub.3 H                                                    2-167 2-CN 4-CF.sub.3                                                                         Me       H                                                    2-168 2-CN 4-CF.sub.3                                                                         Et       H                                                    2-169 2-CN 4-CF.sub.3                                                                         Me       Me                                                   2-170 2-CN 4-CF.sub.3                                                                         Pr.sup.i H                                                    __________________________________________________________________________

Hereunder are ¹ H-NMR(CDCL₃, δppm from TMS) data for the compounds ofthe present invention.

NMR-1 (Compound No. 1-4): 1.26(6H, t), 3.28(3H, s), 3.60(2H, m),3.70(3H, s), 3.86(2H, m), 6.45(1H, s), 7.29(1H, s), 7.50(1H, d),8.21(1H, d)

NMR-2 (Compound No. 1-5): 1.27(6H, t), 1.45(3H, t), 3.31(3H, s),3.63(2H, m), 3.88(2H, m), 4.08(2H, q), 6.47(1H, s), 7.30(1H, s), 7.51),8.23(1H, d)

(Herbicide)

Now, some formulation examples suitable to the herbicide according topresent invention are given hereinbelow. However, the active ingredientsand, types and additional portions of additives contained in suchformulations shall be modified over a wide range and shall not belimited to the ones specified in the examples described below. Partsindicated in the following formulation examples means parts by weight.

EXAMPLE 4

Wettable Powder

    ______________________________________                                        The inventive compound                                                                          20 parts                                                    White carbon      20 parts                                                    Diatomaceous earth                                                                              52 parts                                                    Sodium alkylsulfate                                                                             8 parts                                                     ______________________________________                                    

All materials are uniformly mixed and grinded up to fine powders tothereby obtain a wettable powder formulation containing 20% activeingredient.

EXAMPLE 5

Emulsifiable Concentrate

    ______________________________________                                        The inventive compound  20 parts                                              Xylene                  55 parts                                              Dimethylformamide       15 parts                                              Polyoxyethylenephenyl ether                                                                           10 parts                                              ______________________________________                                    

All materials are mixed and dissolved to obtain an emulsifiableconcentrate formulation containing 20% active ingredient.

EXAMPLE 6

Granules

    ______________________________________                                        The inventive compound                                                                          5 parts                                                     Talc              40 parts                                                    Clay              38 parts                                                    Bentonite         10 parts                                                    Sodium alkylsulfate                                                                             7 parts                                                     ______________________________________                                    

All materials are uniformly mixed, grinded up to fine powders andgranulated into granules having a diameter of from 0.5 to 1.0 mm tothereby obtain a granular formulation containing 5% active ingredient.

Industrial Use of the Invention

Test examples which are carried out to show a herbicidal activity of theherbicides according to the present invention are now describedhereinbelow.

Herbicidal activity is evaluated purauant to the following criterion,and it is expressed as an index for killed-weeds.

    ______________________________________                                        Criterion for assessment                                                      % of Killed-weeds                                                                            Index for Killed-weeds                                         ______________________________________                                         0%            0                                                              20-29%         2                                                              40-49%         4                                                              60-69%         6                                                              80-89%         8                                                              100%           10                                                             ______________________________________                                    

Indexes 1, 3, 5, 7 and 9 represent an intermediate activity between 0and 2, 2 and 4, 4 and 6, 6 and 8, 8 and 10, respectively.

% of Killed-weed= (Weight of fresh weeds growing over the ground innon-treated plot-Weight of fresh weeds growing over the ground in atreated-plot)÷(Weight of fresh weeds growing over the ground innon-treated plot)!×100

Test Example 1

Foliar Application

In a 200 cm² planting pot filled with soil, all seeds of velvet leaf,pigweed, cocklebur, giant foxtail and maize wee planted over its soilsurface, and the seeds were covered with slight amount of soil to growin a greenhouse. When each plants has grown to 5 to 25 cm height,respectively, an emulsion prepared from an emulsifiable concentrateformulation prepared in the example 5 being adjusted at a desiredconcentration by diluting with water was sprayed to thier shoots at avolume rate of 1000 liters/ha by using a small sprayer. 3 weeks later,herbicidal performance and phytotoxicity on maize were checked,respectively, according to the criterion as described above, showing theresults in Table 3.

                  TABLE 3                                                         ______________________________________                                        Compound                                                                              Dose   Velvet                Giant                                    No.     g/ha   leaf    Pigweed                                                                              Cocklebur                                                                            foxtail                                                                             Maize                              ______________________________________                                        1-1     250    10      10     10     10    9                                  1-2     250    10      10     10     10    2                                  1-3     250    8       10     10     10    6                                  1-4     250    10      10     10     10    8                                  1-5     250    10      10     10     10    6                                  2-1     250    8       10     8      10    0                                  2-2     250    9       10     10     10    0                                  2-3     250    8       7      9      10    0                                  ______________________________________                                    

What is claimed is:
 1. A compound of formula (1); ##STR24## wherein R¹,R² are each independently hydrogen, a halogen atom, nitro, cyano, a C₁₋₆alkyl, a C₁₋₆ alkoxy, a C₁₋₆ haloalkyl, a C₁₋₆ haloalkoxy, a C₁₋₆alkylthio, a C₁₋₆ alkylsulfinyl or a C₁₋₆ alkylsulfonyl,R³ is formyl, adi-C₁₋₆ alkoxymethyl or a C₁₋₆ alkylthiomethyl, and R⁴ and R⁵ are eachindependently hydrogen, a C₁₋₆ alkyl, a C₁₋₆ haloalkyl, a C₂₋₆ alkenyl,C₂₋₆ alkynyl or a C₃₋₈ cycloalkyl, and a salt thereof.
 2. A herbicidecomprising one or more of compounds of formula (1); ##STR25## whereinR¹, R², R³, R⁴ and R⁵ are as defined above, or the salts thereof as itsactive component(s).